Scintillators and applications thereof

ABSTRACT

Scintillators of various constructions and methods of making and using the same are provided. In some embodiments, a scintillator comprises at least one radiation absorption region and at least one spatially discrete radiative exciton recombination region.

RELATED APPLICATION DATA

The present application hereby claims priority under 35 U.S.C. §119(e)to U.S. Patent Application Ser. No. 61/325,688, filed Apr. 19, 2010,which is hereby incorporated by reference in its entirety.

STATEMENT OF GOVERNMENT LICENSE RIGHTS

This invention was made with Government support under Grant No.DE-AC02-05CH11231 awarded by the United States Department of Energy. TheGovernment has certain rights in the invention.

FIELD OF THE INVENTION

The present invention relates to luminescent materials and, inparticular, to scintillators and applications thereof.

BACKGROUND OF THE INVENTION

Scintillators are materials that absorb high-energy radiation (e.g.gamma rays, x-rays, high-energy particles) and emit light (low-energyphotons) in response. To the extent that the number of emitted photonsis proportional to the total energy of the stopped radiation, ascintillator provides the useful function of identifying the totalenergy of any radiation that is stopped.

As the nucleus of every element (and each isotope of each element) emitsa characteristic fingerprint of gamma-ray energies when suitably excited(usually by neutron activation), scintillator responses to suchemissions provide value in security screening of shipping and truckingcontainers and baggage, where chemical elements and isotopes of elementscan be identified (and imaged using arrays of segmented scintillators)without opening the container. This applies both to radioactive elements(nuclear nonproliferation and screening) and to ordinary non-radioactiveelements via neutron activation of gamma emission. Scintillators arealso widely used in medical imaging and diagnostics as well as oil-welllogging, where energy resolution can often also be of value. Desirableenergy resolution requires sufficient proportionality of light yield toray energy. Non-proportionality of scintillator photonic emission to thestopped radiation can degrade resolution and produce significantinaccuracies in determining the total energy of the radiation received.

It is generally accepted that non-proportionality in scintillators isassociated with quenching (non-radiative electron-hole recombination) inparts of the particle/ray track wherein ionization density is high,coupled with the characteristic variability of dE/dx from beginning toend of an electron track. Prior scintillators, such as CsI:Tl as well asothers, comprise crystalline materials doped with impurities. Theimpurities serve as radiative recombination centers for electron-holepairs generated from the absorption of the high energy radiation.Impurities are doped throughout the host crystal to ensure efficientphotonic output from the scintillator upon radiation absorption. As aresult, an electron-hole pair does not have to travel far beforecontacting an impurity for radiative recombination. This limitation ofcarrier mobilities reduces the probability of linear (i.e. trapdominated) non-radiative electron-hole recombination, thereby maximizingthe light output of the scintillator. Maximization of light output bythis route, however, has associated costs as the limitation of carriermobility by high dopant levels throughout the host crystal can result inor exacerbate non-proportional response of the scintillator to theabsorbed radiation.

SUMMARY

In view of the foregoing, scintillators are described herein which, insome embodiments, may address one or more disadvantages of previousscintillators. In some embodiments, a scintillator described hereincomprises at least one radiation absorption or stopping region and atleast one spatially discrete radiative exciton recombination region forreceiving excitons from the at least one radiation absorption region. Insome embodiments, a scintillator described herein comprises a pluralityof radiation absorption regions and a plurality of spatially discreteradiative exciton recombination regions for receiving excitons from theplurality of radiation absorption regions.

In some embodiments, a radiative exciton recombination region operableto receive excitons from a radiation absorption region comprises one ormore scintillation activators. In some embodiments of a scintillatordescribed herein, a radiation absorption region comprises lessscintillation activator than one or more spatially discrete radiativeexciton recombination regions. In some embodiments, a radiationabsorption region is free or substantially free of scintillationactivator.

Exciton(s), as used herein, refers to bound electron-hole pairs as wellas free or independent holes and electrons. Additionally, radiationincludes electromagnetic radiation, particle radiation, photons,electrons, heavy charged particles, neutrons or combinations thereof. Insome embodiments, radiation comprises high energy radiation such asgamma rays, x-rays, other high energy particles or combinations thereof.

In some embodiments, a scintillator described herein comprises asingle-crystalline material. In some embodiments, a scintillatordescribed herein comprises a polycrystalline material. In someembodiments, a scintillator described herein is optically transparent orsubstantially optically transparent.

Moreover, in some embodiments, a radiation absorption region of ascintillator described herein comprises one or more metal halides. Inembodiments described herein, a metal halide comprises an alkali halide,an alkaline earth halide or a transition metal halide or mixturesthereof. In some embodiments, a metal halide absorption region of ascintillator comprises less scintillation activator than one or morespatially discrete radiative exciton recombination regions. In someembodiments, a metal halide absorption region of a scintillator is freeor substantially free of scintillation activator. In some embodiments, aradiation absorption region of a scintillator described herein comprisesa semiconductor material including, but not limited to, II/VIsemiconductors and/or III/V semiconductors.

In some embodiments, a spatially discrete radiative excitonrecombination region comprises a metal halide having incorporatedtherein one or more scintillation activators. In some embodiments,scintillation activators comprise transition metals, lanthanide serieselements or actinide series elements or combinations thereof. In someembodiments, one or more scintillation activators can comprise dopants,impurities or intrinsic defects within the crystalline structure of themetal halide. In some embodiments, a spatially discrete radiativeexciton recombination region comprises a semiconductor material having abandgap less than the bandgap of a semiconductor material of theradiation absorption region. In some embodiments, a semiconductormaterial of a spatially discrete radiative recombination regioncomprises a II/VI semiconductor or a III/V semiconductor.

In another aspect, crystalline particles or grains are provided. In someembodiments, crystalline particles or grains can be sintered to providea scintillator having a construction described herein. A crystallineparticle or grain, in some embodiments, comprises a radiation absorptionregion comprising at least one metal halide and a spatially discreteradiative exciton recombination region. In some embodiments, thespatially discrete radiative exciton recombination region comprises ametal halide comprising one or more scintillation activators. In someembodiments, a metal halide absorption region comprises lessscintillation activator than one or more spatially discrete radiativeexciton recombination regions. In some embodiments, a metal halideabsorption region is free or substantially free of scintillationactivator.

In other embodiments, a crystalline particle or grain comprises at leastone radiation absorption region and at least one spatially discreteradiative exciton recombination region, the particle having a sizeranging from about 20 nm to about 1 μm. In some embodiments, the atleast one radiation absorption region of the crystalline particlecomprises a metal halide free or substantially free of a scintillationactivator, and the at least one radiative exciton recombination regioncomprises a metal halide comprising one or more scintillationactivators. In some embodiments, the at least one radiation absorptionregion comprises a first semiconductor having a first bandgap, and theat least one radiative exciton recombination region comprises a secondsemiconductor having a second bandgap. In some embodiments, the secondbandgap is smaller than the first bandgap.

In another embodiment, a scintillation detector or counter is describedherein. In some embodiments, a scintillation detector or countercomprises a scintillator and an electromagnetic radiation sensor,wherein the scintillator comprises any construction described herein. Insome embodiments, for example, a scintillator of a scintillationdetector has a construction comprising at least one radiation absorptionregion and at least one spatially discrete radiative excitonrecombination region comprising a scintillation activator, whereinexcitons are received from the at least one radiation absorption region.

In another aspect, methods of making scintillators are described herein.In some embodiments, a method of making a scintillator comprisesproviding a radiation absorption region comprising a first materialhaving a first bandgap and locally modulating the first bandgap to trapexcitons in a spatially discrete radiative exciton recombination region,wherein locally modulating the first bandgap comprises providing theradiative exciton recombination region in electrical communication withthe radiation absorption region. In some embodiments, the first materialcomprises a metal halide and the second material comprises a metalhalide having incorporated therein one or more scintillation activators.In some embodiments, the metal halide first material is free orsubstantially free of scintillation activator.

A method of producing a scintillator, in some embodiments, comprisesproviding a radiation absorption region comprising a metal halide andproviding a spatially discrete radiative exciton recombination region inelectrical communication with the radiation absorption region, theradiative exciton recombination region comprising a metal halidecomprising one or more scintillation activators. In some embodiments,the metal halide radiation absorption region comprises lessscintillation activator than the spatially discrete radiative excitonrecombination region. In some embodiments, the metal halide radiationabsorption region is free or substantially free of scintillationactivator.

In some embodiments, a method of producing a scintillator comprisesproviding a mixture of metal halide particles and metal halide particlescomprising one or more scintillation activators and sintering theparticles of the mixture to provide a polycrystalline scintillator. Insome embodiments, the polycrystalline scintillator comprises a radiationabsorption region formed from sintered metal halide particles free orsubstantially free of scintillation activator. Moreover, in someembodiments, the polycrystalline scintillator comprises spatiallydiscrete radiative exciton recombination regions formed from the metalhalide particles comprising one or more scintillation activators. Insome embodiments, for example, metal halide particles comprising one ormore scintillation activators are dispersed throughout a sintered matrixof metal halide particles free or substantially free of scintillationactivator to provide spatially discrete radiative exciton recombinationregions.

In some embodiments, a method of producing a scintillator comprisesproviding crystalline particles comprising a radiation absorption regionand a spatially discrete radiative recombination region and sinteringthe crystalline particles to provide a polycrystalline scintillator. Insome embodiments, the radiation absorption region of a crystallineparticle comprises a metal halide free or substantially free ofscintillation activator, and the spatially discrete radiativerecombination region comprises a metal halide comprising one or morescintillation activators. In some embodiments, the radiation absorptionregion of a crystalline particle comprises a first semiconductor havinga first bandgap, and the spatially discrete radiative recombinationregion comprises a second semiconductor having a second bandgap. In someembodiments, the second bandgap is less than the first bandgap.

In another aspect, methods of converting radiation of a first energyinto radiation of a second energy are described herein. In oneembodiment, a method of converting radiation of a first energy intoradiation of a second energy comprises providing a scintillatorcomprising at least one radiation absorption region and at least onespatially discrete radiative exciton recombination region, absorbing theradiation of the first energy in the radiation absorption region togenerate excitons and recombining at least some of the excitons in thespatially discrete radiative exciton recombination region to emitradiation of a second energy. In some embodiments, the radiation of thefirst energy has a wavelength less than the wavelength of the radiationof the second energy. As described herein, in some embodiments, theradiation absorption region of the scintillator comprises a metalhalide, and the spatially discrete radiative exciton recombinationregion comprises a metal halide comprising one or more scintillationactivators. In some embodiments, the metal halide radiation absorptionregion comprises less scintillation activator than one or more spatiallydiscrete radiative exciton recombination regions. In some embodiments,the metal halide radiation absorption region is free or substantiallyfree of scintillation activator.

In a further aspect, methods of reducing non-proportional response in ascintillator are described herein. In one embodiment, a method ofreducing non-proportional response comprises providing a scintillatorcomprising at least one radiation absorption region and at least onespatially discrete radiative exciton recombination region, absorbingradiation of a first energy in the radiation absorption region togenerate excitons, transferring at least some of the excitons out of theradiation absorption region and into the spatially discrete radiativeexciton recombination region and recombining the excitons to emitradiation of a second energy from the radiative exciton recombinationregion. In some embodiments, the radiation absorption region of thescintillator comprises a metal halide free or substantially free of ascintillation activator, and the spatially discrete radiative excitonrecombination region comprises a metal halide comprising one or morescintillation activators.

These and other embodiments are described in greater detail in thedetailed description which follows.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates spatially discrete radiation absorption and radiativeexciton recombination regions of a scintillator according to oneembodiment described herein.

FIG. 2 illustrates spatially discrete radiation absorption and radiativeexciton recombination regions of a scintillator according to oneembodiment described herein.

FIG. 3 illustrates spatially discrete radiation absorption and radiativeexciton recombination regions of a scintillator according to oneembodiment described herein.

FIG. 4 illustrates a crystalline particle according to one embodimentdescribed herein.

FIG. 5 illustrates a crystalline particle according to one embodimentdescribed herein.

FIG. 6 illustrates a scintillator and the associated electronicstructure according to one embodiment described herein.

DETAILED DESCRIPTION

The present invention can be understood more readily by reference to thefollowing detailed description and drawings and their previous andfollowing descriptions. Elements, apparatus and methods of the presentinvention, however, are not limited to the specific embodimentspresented in the detailed description and drawings. It should berecognized that these embodiments are merely illustrative of theprinciples of the present invention. Numerous modifications andadaptations will be readily apparent to those of skill in the artwithout departing from the spirit and scope of the invention.

As described herein, the present invention provides scintillators andmethods of making and using the same. In some embodiments, ascintillator comprises at least one radiation absorption region and atleast one spatially discrete radiative exciton recombination region forreceiving excitons from the at least one radiation absorption region. Insome embodiments, a scintillator comprises a plurality of radiationabsorption regions and a plurality of spatially discrete radiativeexciton recombination regions for receiving excitons from the pluralityof radiation absorption regions.

In keeping radiation absorption and radiative exciton recombinationregions spatially discrete, at least some, if not substantially all,excitons generated in one or more radiation absorption regions aretransferred to one or more radiative exciton recombination regions forrecombination and photonic emission. As described herein, the absence ofscintillation activator in the radiation absorption material facilitatestransfer of excitons out of the absorption material to the radiativeexciton recombination material. A scintillator architecture wherein aradiation absorption or stopping region is spatially discrete from anexciton recombination region is a fundamental departure from priorscintillator constructions wherein radiation absorption and excitonrecombination occur in the same region or material. Prior scintillatorconstructions, for example, utilize a radiation absorption materialdoped throughout with impurities (scintillation activators) to induceradiative exciton recombination throughout the absorption material.

FIG. 1 illustrates spatially discrete radiation absorption and radiativeexciton recombination regions of a scintillator according to oneembodiment described herein. The scintillator (100) illustrated in FIG.1 comprises a plurality of radiation absorption or stopping regions(102) and a plurality of spatially discrete radiative excitonrecombination regions (104). In the embodiment illustrated in FIG. 1,the spatially discrete radiative exciton recombination regions (104) aredisposed as continuous layers between layered radiation absorptionregions (102). As provided herein, excitons generated in the radiationabsorption layers (102) are transferred to the radiative excitonrecombination regions (104) for recombination and light emission.

FIG. 2 illustrates spatially discrete radiation absorption and radiativeexciton recombination regions of a scintillator according to anotherembodiment described herein. The scintillator illustrated in FIG. 2comprises a plurality of radiation absorption or stopping regions (202)and a plurality of spatially discrete radiative exciton recombinationregions (204). The spatially discrete radiative exciton recombinationregions (204) are disposed as discontinuous layers of island structurespositioned between layers of radiation absorption regions (202). The useof island structures for spatially discrete radiative excitonrecombination regions (204), in some embodiments, permits excitonsproduced in the radiation absorption regions (202) to be confined in3-dimensions.

FIG. 3 illustrates spatially discrete radiation absorption and radiativeexciton recombination regions of a scintillator according to anotherembodiment described herein. The scintillator illustrated in FIG. 3comprises a continuous radiation absorption or stopping region (302) anda plurality of spatially discrete radiative exciton recombinationregions (304). The spatially discrete radiative exciton recombinationregions (304) are island structures disposed in the radiation absorptionregion (302). In some embodiments, the radiative exciton recombinationregions (304) are randomly ordered in and/or dispersed throughout theradiation absorption region (302). In some embodiments, the radiativeexciton recombination regions (304) are patterned in the radiationabsorption region.

A spatially discrete radiative exciton recombination region, in someembodiments, occupies a fraction of the space or volume occupied by aradiation absorption region. In some embodiments of a layeredscintillator, such as that illustrated in FIG. 1 or FIG. 2 herein, thethickness ratio of a radiation absorption region to a radiative excitonrecombination region is at least 10. In some embodiments, the thicknessratio of a radiation absorption region to a radiative excitonrecombination region is at least 100. The thickness ratio of a radiationabsorption region to a radiative exciton recombination region, in someembodiments, is at least 1000. In some embodiments, the thickness ratioof a radiation absorption region to a radiative exciton recombinationregion is at least 10,000.

In some embodiments, spatially discrete radiative exciton recombinationregions of a scintillator described herein have a spacing equal orsubstantially equal to the diffusion range of the least mobile carriersgenerated in the radiation absorption region. In some embodiments,spatially discrete radiative exciton recombination regions have aspacing less than the diffusion range of the least mobile carriersgenerated in the radiation absorption region. In some embodiments, theleast mobile carriers generated in the radiation absorption region areholes. In some embodiments, the least mobile charge carriers generatedin the radiation absorption region are electrons.

As carrier mobility and carrier diffusion range varies from material tomaterial, spacing of spatially discrete radiative exciton recombinationregions can vary depending on the identity of the material of theradiation absorption region. In some embodiments, diffusion range of acarrier of a radiation absorption region is determined according to:r=(Dt)^(0.5)wherein D is the diffusion coefficient of the material forming theradiation absorption region and wherein D is related to carrier mobility(μ) by:D=kT μ/ewherein k is the Boltzman constant, T is temperature (K) and e iselectron charge. With the carrier diffusion range of a radiationabsorption region being determined according to the foregoing, theappropriate spacing of spatially discrete exciton recombination regionsfor a scintillator described herein can be set.

In some embodiments, a radiation absorption region comprises one or morematerials having a carrier (hole or electron) mobility of at least about1·10⁻⁴ cm²/V·s. In some embodiments, a material of a radiationabsorption region has a carrier mobility of at least about 1·10³ cm²/V·sor at least about 0.1 cm²/V·s. In some embodiments, a material of aradiation absorption region has a carrier mobility of at least 1cm²/V·s. In some embodiments, a material of a radiation absorptionregion has a carrier mobility of at least 100 cm²/V·s or at least 1000cm²/V·s.

In some embodiments, a material of a radiation absorption region has acarrier mobility ranging from about 1·10⁻⁴ cm²/V·s to about 1000cm²/V·s. In some embodiments, a material of a radiation absorptionregion has a carrier mobility ranging from about 1·10⁻² cm²/V·s to about100 cm²/V·s. In some embodiments, a material of a radiation absorptionregion has a carrier mobility ranging from about 0.1 cm²/V·s to about 70cm²/V·s or from about 1 cm²/V·s to about 50 cm²/V·s. In someembodiments, a material of a radiation absorption region has a carriermobility ranging from about 5 cm²/V·s to about 100 cm²/V·s or from about10 cm²/V·s to about 75 cm²/V·s. In some embodiments, a material of aradiation absorption region has a carrier mobility ranging from about 20cm²/V·s to about 80 cm²/V·s.

I. Metal Halide Scintillator

In some embodiments, a scintillator described herein comprises at oneradiation absorption region comprising a metal halide and at least onespatially discrete radiative exciton recombination region comprising ametal halide comprising one or more scintillation activators. In someembodiments, the metal halide of the radiation absorption region is freeor substantially free of scintillation activator, thereby promoting thetransfer of one or more photo-generated charge carriers or excitons to aspatially discrete radiative exciton recombination region forrecombination and photonic emission.

A. Alkali Halide Scintillators

In some embodiments, metal halides suitable for use as the radiationabsorption region of a scintillator described herein comprise alkalihalides. In some embodiments, for example, a radiation absorption regioncomprises cesium iodide (CsI), sodium iodide (NaI) or potassium iodide(KI). In some embodiments, an alkali halide radiation absorption regioncomprises less scintillation activator than an alkali halide spatiallydiscrete radiative exciton recombination region described herein. Insome embodiments, an alkali halide radiation absorption region is freeor substantially free of scintillator.

Moreover, in some embodiments, metal halides suitable for use in aspatially discrete radiative exciton recombination region comprisealkali halides comprising one or more scintillation activatorsassociated therewith. In some embodiments, a spatially discreteradiative exciton recombination region comprises CsI, NaI or KIcomprising one or more scintillation activators. In some embodiments, aspatially discrete radiative exciton recombination region and aradiation absorption region comprise the same alkali halide. In someembodiments, a spatially discrete radiative exciton recombination regionand a radiation absorption region comprise different alkali halides. Insome embodiments comprising different alkali halides, the alkali halideof the spatially discrete radiative exciton recombination region has alower bandgap than the alkali halide of the radiation absorption region.In some embodiments wherein the alkali halide of the spatially discreteradiative exciton recombination region has a lower bandgap, the alkalihalide of the recombination region does not comprise a scintillationactivator.

As described herein, scintillation activators can comprise transitionmetals, lanthanide series elements, actinide series elements, alkalimetals, impurities, intrinsic crystalline defects or combinationsthereof. In some embodiments, a scintillation activator of an alkalihalide comprises thallium (Tl⁺) or sodium (Na⁺)

An alkali halide spatially discrete radiative exciton recombinationregion can comprise any amount of scintillation activator notinconsistent with the objectives of the present invention. In someembodiments, an alkali halide spatially discrete radiative excitonrecombination region comprises one or more scintillation activators inan amount of at least about 0.1 mol %. In some embodiments, an alkalihalide spatially discrete radiative exciton recombination regioncomprises one or more scintillation activators in an amount of at leastabout 0.3 mol %. In some embodiments, an alkali halide spatiallydiscrete radiative exciton recombination region comprises one or morescintillation activators in an amount of at least about 0.5 mol %. Insome embodiments, an alkali halide spatially discrete radiative excitonrecombination region comprises one or more scintillation activators inan amount ranging from about 0.1 mol % to about 1 mol %.

In some embodiments, spatially discrete radiative exciton recombinationregions are incorporated into a single crystal radiation absorption hostof an alkali halide. In some embodiments described further herein,spatially discrete radiative exciton recombination regions are providedas alkali halide particles doped with one or more scintillationactivators. The doped alkali halide particles are mixed with undopedalkali halide particles and co-sintered to provide a polycrystallinescintillator material, wherein the undoped alkali halide particles formone or more radiation absorption regions of the polycrystallinescintillator. Additionally, in some embodiments described furtherherein, alkali halide particles comprising at least one radiationabsorption region and at least one spatially discrete radiative excitonrecombination region are provided and sintered resulting in apolycrystalline scintillator.

Moreover, in some embodiments of a scintillator described herein havinga radiation absorption region comprising an alkali halide, the spatiallydiscrete radiative exciton recombination regions have a spacing of up toabout 40 nm. In some embodiments, the spatially discrete radiativeexciton combination regions have spacing of up to about 30 nm or 20 nm.In some embodiments, the spatially discrete radiative excitonrecombination regions have a spacing ranging from about 1 nm to about 40nm or from about 5 nm to about 30 nm. In some embodiments, the spatiallydiscrete radiative exciton recombination regions have a spacing rangingfrom about 10 nm to about 20 nm.

B. Alkaline Earth Halide Scintillators

In some embodiments, metal halides suitable for use as the radiationabsorption region of a scintillator described herein comprise alkalineearth halides. In some embodiments, for example, a radiation absorptionregion comprises strontium iodide (SrI₂), barium iodide (BaI₂) or bariumbromide iodide (BaBrI). In some embodiments, an alkaline earth halideradiation absorption region comprises less scintillation activator thanan alkaline earth halide spatially discrete radiative excitonrecombination region described herein. In some embodiments, an alkalineearth halide radiation absorption region is free or substantially freeof scintillator.

Additionally, in some embodiments, metal halides suitable for use in aspatially discrete radiative exciton recombination region comprisealkaline earth halides comprising one or more scintillation activatorsassociated therewith. In some embodiments, a spatially discreteradiative exciton recombination region comprises SrI₂, BaI₂ or BaBrIcomprising one or more scintillation activators. In some embodiments, aspatially discrete radiative exciton recombination region and aradiation absorption region comprise the same alkaline earth halide. Insome embodiments, a spatially discrete radiative exciton recombinationregion and a radiation absorption region comprise different alkalineearth halides. In some embodiments comprising different alkaline earthhalides, the alkaline earth halide of the spatially discrete radiativeexciton recombination region has a lower bandgap than the alkaline earthhalide of the radiation absorption region. In some embodiments whereinthe alkaline earth halide of the spatially discrete radiative excitonrecombination region has a lower bandgap, the alkaline earth halide ofthe recombination region does not comprise a scintillation activator.

As described herein, scintillation activators can comprise transitionmetals, lanthanide series elements, actinide series elements, alkalimetals, impurities, intrinsic crystalline defects or combinationsthereof. In some embodiments, a scintillation activator of an alkaliearth halide comprises europium (Eu²⁺).

An alkaline earth halide spatially discrete radiative excitonrecombination region can comprise any amount of scintillation activatornot inconsistent with the objectives of the present invention. In someembodiments, an alkaline earth halide spatially discrete radiativeexciton recombination region comprises one or more scintillationactivators in an amount of at least about 0.1 mol %. In someembodiments, an alkaline earth halide spatially discrete radiativeexciton recombination region comprises one or more scintillationactivators in an amount of at least about 0.3 mol %. In someembodiments, an alkaline earth halide spatially discrete radiativeexciton recombination region comprises one or more scintillationactivators in an amount of at least about 0.5 mol %. In someembodiments, an alkaline earth halide spatially discrete radiativeexciton recombination region comprises one or more scintillationactivators in an amount ranging from about 0.1 mol % to about 10 mol %or from about 1 mol % to about 10 mol %. In some embodiments, analkaline earth halide spatially discrete radiative exciton recombinationregion comprises one or more scintillation activators in an amountranging from about 2 mol % to about 8 mol % or from about 3 mol % toabout 7 mol %.

In some embodiments, spatially discrete radiative exciton recombinationregions are incorporated into a single crystal radiation absorption hostof an alkaline earth halide. In some embodiments described furtherherein, spatially discrete radiative exciton combination regions areprovided as alkaline earth halide particles doped with one or morescintillation activators. The doped alkaline earth halide particles aremixed with undoped alkaline earth halide particles and co-sintered toprovide a polycrystalline scintillator material, wherein the undopedalkaline earth halide particles form one or more radiation absorptionregions of the polycrystalline scintillator. Additionally, in someembodiments described further herein, alkaline earth halide particlescomprising at least one radiation absorption region and at least onespatially discrete radiative exciton recombination region are providedand sintered resulting in a polycrystalline scintillator.

In some embodiments of a scintillator described herein having aradiation absorption region comprising an alkaline earth halide, thespatially discrete radiative exciton recombination regions have aspacing of up to about 500 nm. In some embodiments, the spatiallydiscrete radiative exciton recombination regions have spacing of up toabout 200 nm or 100 nm. In some embodiments, the spatially discreteradiative exciton recombination regions have a spacing ranging fromabout 10 nm to about 500 nm or from about 50 nm to about 200 nm. In someembodiments, the spatially discrete radiative exciton recombinationregions have a spacing ranging from about 5 nm to about 200 nm or fromabout 10 nm to about 100 nm.

C. Transition Metal Halide Scintillators

In some embodiments, metal halides suitable for use as the radiationabsorption region of a scintillator described herein comprise transitionmetal halides. In some embodiments, for example, a radiation absorptionregion comprises a transition metal halide, wherein the metal isselected from the group consisting of metallic elements of Groups IB,IIB, IIIB, IIIA, IVA and VA of the Periodic Table. Groups of thePeriodic Table described herein are identified according to the CASdesignation. In some embodiments, for example, the radiation absorptionregion comprises a lanthanum halide, copper halide, zinc halide, cadmiumhalide, mercury halide, indium halide, thallium halide, tin halide or alead halide. In some embodiments, the radiation absorption regioncomprises LaBr₃, LaCl₃, CuI, ZnI₂, CdI₂, HgI₂, InI, TlI, SnI₄ or PbI₂.

In some embodiments, a transition metal halide radiation absorptionregion comprises less scintillation activator than a transition metalhalide spatially discrete radiative exciton recombination regiondescribed herein. In some embodiments, a transition metal halideradiation absorption region is free or substantially free ofscintillator.

In some embodiments, a spatially discrete radiative excitonrecombination region and a radiation absorption region comprise the sametransition metal halide. In some embodiments, a spatially discreteradiative exciton recombination region and a radiation absorption regioncomprise different transition metal halides. In some embodimentscomprising different transition metal halides, the transition metalhalide of the spatially discrete radiative exciton recombination regionhas a lower bandgap than the transition metal halide of the radiationabsorption region. In some embodiments wherein the transition metalhalide of the spatially discrete radiative exciton recombination regionhas a lower bandgap, the transition metal halide of the recombinationregion does not comprise a scintillation activator.

In some embodiments, metal halides suitable for use in a spatiallydiscrete radiative exciton recombination region comprise transitionmetal halides comprising one or more scintillation activators associatedtherewith. In some embodiments, for example, a spatially discreteradiative exciton recombination region comprises a transition metalhalide comprising one or more scintillation activators, wherein thetransition metal is selected from the group consisting of metallicelements of Groups IB, IIB, IIIB, IIIA, IVA and VA of the PeriodicTable. In some embodiments, a spatially discrete radiative excitonrecombination region comprises a lanthanum halide, copper halide, zinchalide, cadmium halide, mercury halide, indium halide, thallium halide,tin halide or a lead halide. In some embodiments, the radiationabsorption region comprises LaBr₃, LaCl₃, CuI, ZnI₂, CdI₂, HgI₂, InI,TlI, SnI₄ or PbI₂ comprising one or more scintillation activators. Insome embodiments, a spatially discrete radiative exciton recombinationregion and a radiation absorption region comprise the same transitionmetal halide. In some embodiments, a spatially discrete radiativeexciton recombination region and a radiation absorption region comprisedifferent transition halides.

As described herein, scintillation activators can comprise transitionmetals, lanthanide series elements, actinide series elements, alkalimetals, impurities, intrinsic crystalline defects or combinationsthereof. In some embodiments, a scintillation activator comprises cerium(Ce³⁺) for use in a lanthanum halide (e.g. LaBr₃ or LaCl₃) excitonrecombination region. In some embodiments, cerium can be present in aspatially discrete lanthanum halide exciton recombination region in anamount ranging from about 0.1 mol % to about 30 mol %. In someembodiments, a scintillation activator comprises one or more impuritiesand/or defects in the crystalline structure of a transition metal halideof a spatially discrete recombination region.

In some embodiments, spatially discrete radiative exciton recombinationregions are incorporated into a single crystal radiation absorption hostof a transition metal halide. In some embodiments described furtherherein, spatially discrete radiative exciton recombination regions areprovided as transition metal halide particles having one or morescintillation activators. These transition metal halide particles aremixed with transition metal halide particles substantially free ofscintillation activator and co-sintered to provide a polycrystallinescintillator material, wherein the activator free transition metalhalide particles form one or more radiation absorption regions of thepolycrystalline scintillator. Additionally, in some embodimentsdescribed further herein, transition metal halide particles comprisingat least one radiation absorption region and at least one spatiallydiscrete radiative exciton recombination region are provided andsintered resulting in a polycrystalline scintillator.

In some embodiments of a scintillator described herein having aradiation absorption region comprising a transition metal halide, thespatially discrete radiative exciton recombination regions have aspacing of up to about 5 μM. In some embodiments, the spatially discreteradiative exciton recombination regions have a spacing ranging fromabout 10 nm to about 5 μm or from about 100 nm to about 1 μm. In someembodiments, the spatially discrete radiative exciton recombinationregions have a spacing ranging from about 250 nm to about 750 nm.

II. Polycrystalline Scintillators

In another aspect, polycrystalline scintillators are described herein.In some embodiments, a scintillator comprises a polycrystallinematerial, the polycrystalline material having at least one radiationabsorption region and at least one spatially discrete radiative excitonrecombination region. In some embodiments, the polycrystalline materialof a scintillator comprises a plurality of radiation absorption regionsand/or a plurality of spatially discrete radiative exciton recombinationregions.

In some embodiments, the at least one radiation absorption regioncomprises one or more crystalline grains free or substantially free ofscintillation activator. Moreover, in some embodiments, the at least onespatially discrete radiative exciton recombination region comprises oneor more crystalline grains comprising a scintillation activator. In someembodiments, one or more spatially discrete radiative recombinationregions of a polycrystalline scintillator comprises more scintillationactivator than a radiation absorption region.

In some embodiments, crystalline grains comprising scintillationactivator are present in a polycrystalline scintillator described hereinin an amount of up to about 30 weight percent. In some embodiments,crystalline grains comprising scintillation activator are present in anamount ranging from about 0.01 weight percent to about 30 weight percentor from about 0.1 weight percent to about 20 weight percent. In someembodiments, crystalline grains comprising scintillation activator arepresent in an amount ranging from about 1 weight percent to about 10weight percent.

In some embodiments wherein a radiation absorption region comprisescrystalline grains and spatially discrete radiative excitonrecombination regions comprise crystalline grains, the polycrystallinescintillator material is a sintered material. In some embodiments, forexample, crystalline grains of a radiation absorption region form asintered host matrix in which crystalline grains comprisingscintillation activator are dispersed. The dispersed crystalline grainscomprising scintillation activator provide the spatially discreteradiative exciton recombination regions.

In some embodiments, a polycrystalline scintillator material describedherein has a density of at least about 95% of theoretical density (i.e.,the density of a single crystal). In some embodiments, a polycrystallinescintillator material described herein has a density of at least about97%. In some embodiments, a polycrystalline scintillator describedherein has a density of at least about 99%.

In some embodiments, crystalline grains of a radiation absorption regionand crystalline grains of spatially discrete radiative excitonrecombination regions comprise one or more alkali halides as set forthin section IA hereinabove. In some embodiments, alkali halidecrystalline grains of a radiation absorption region have an average sizeless than about 40 nm. In some embodiments, alkali halide crystallinegrains of a radiation absorption region have an average size rangingfrom about 1 nm to about 40 nm or from about 10 nm to about 20 nm.

In some embodiments, crystalline grains of a radiation absorption regionand crystalline grains of spatially discrete radiative excitonrecombination regions comprise one or more alkaline earth halides as setforth in section IB hereinabove. In some embodiments, crystalline grainsof one or more alkaline earth halides have a non-cubic crystallinestructure. In some embodiments, alkaline earth halides for use in apolycrystalline scintillator demonstrate an orthorhombic crystallinestructure. In some embodiments, for example, SrI₂, BaI₂ and BaBrIdemonstrate orthorhombic crystalline structures.

In some embodiments, alkali earth halide crystalline grains of aradiation absorption region have an average size less than about 500 nm.In some embodiments, alkaline earth halide crystalline grains of aradiation absorption region have an average size ranging from about 10nm to about 500 nm or from about 50 nm to about 200 nm. In someembodiments, alkaline earth halide crystalline grains of a radiationabsorption region have an average size ranging from about 10 nm to about100 nm.

In some embodiments, crystalline grains of a radiation absorption regionand crystalline grains of spatially discrete radiative excitonrecombination regions comprise one or more transition metal halides asset forth in section IC hereinabove. In some embodiments, crystallinegrains of one or more transition metal halides have a cubic crystallinestructure. In some embodiments, crystalline grains of one or moretransition metal halides have a non-cubic crystalline structure. In someembodiments, transition metal halides for use in a polycrystallinescintillator demonstrate a tetragonal or rhombohedral crystallinestructure. In some embodiments, for example, SnI₄ and PbI₂ demonstraterhombohedral crystalline structures.

In some embodiments, transition metal halide crystalline grains of aradiation absorption region have an average size less than about 5 μm.In some embodiments, transition metal halide crystalline grains of aradiation absorption region have an average size ranging from about 10nm to about 5 μm or from about 100 nm to about 1 μm. In someembodiments, transition metal halide crystalline grains of a radiationabsorption region have an average size ranging from about 250 nm toabout 750 nm.

In some embodiments, crystalline grains of a radiation absorption regionand crystalline grains of spatially discrete radiative excitonrecombination regions comprise one or more semiconductor materials. Insome embodiments, crystalline grains of a radiation absorption regioncomprises a first semiconductor having a first bandgap, and crystallinegrains of spatially discrete radiative exciton recombination regionscomprise a second semiconductor having a second bandgap, wherein thefirst bandgap is greater than the second bandgap.

In some embodiments, the first and/or second semiconductor materialcomprises a binary semiconductor. Binary semiconductors, in someembodiments, comprise II/VI semiconductors, III/V semiconductors orcombinations thereof. In some embodiments, the first and/or secondsemiconductor material comprises ternary or quaternary semiconductoralloys. Ternary or quaternary semiconductor alloys, in some embodiments,comprise III/V alloys, II/VI alloys or combinations thereof.

In some embodiments, semiconductor crystalline grains of a radiationabsorption region have an average size of less than about 100 μm. Insome embodiments, semiconductor crystalline grains of a radiationabsorption region have an average size ranging from about 10 nm to about10 μm or from about 50 nm to about 1 μm. In some embodiments,semiconductor crystalline grains of a radiation absorption region havean average size ranging form about 100 nm to about 750 nm.

In some embodiments, a method of producing a polycrystallinescintillator comprises providing a mixture comprising metal halideparticles free or substantially free of one or more scintillationactivators and metal halide particles comprising one or morescintillation activators and sintering the mixture to provide apolycrystalline scintillator material comprising a radiation absorptionregion and spatially discrete radiative exciton recombination regions.In some embodiments, the radiation absorption region is formed from themetal halide particles free or substantially free of scintillationactivator. In some embodiments, spatially discrete radiative excitonrecombination regions are formed by metal halide particles comprisingone or more scintillation activators. Metal halide particles suitablefor use in methods of forming a polycrystalline scintillator cancomprise any metal halide described herein.

In some embodiments, metal halide particles comprising one or morescintillation activators are present in the mixture in an amount up toabout 30 weight percent. In some embodiments, metal halide particlescomprising scintillation activator are present in the mixture in anamount ranging from about 0.01 weight percent to about 30 weight percentor from about 0.1 weight percent to about 20 weight percent. In someembodiments, metal halide particles comprising scintillation activatorare present in the mixture an amount ranging from about 1 weight percentto about 10 weight percent.

The mixture of metal halide particles can be sintered under anyconditions of temperature, pressure and time effective to provide asintered polycrystalline scintillator having a construction describedherein. Sintering conditions can be determined according to severalfactors including specific identity of the metal halide, particle sizeand particle shape.

In some embodiments, for example, metal halide particles are sintered ata temperature below the melting point of the particles. In someembodiments, metal halide particles described herein are sintered at atemperature ranging from about 30° C. to about 650° C. In someembodiments, sintering temperature can be ramped at any desired rate. Insome embodiments, the temperature is ramped at a rate ranging from about1° C./min to about 10° C./min.

Moreover, in some embodiments, metal halide particles are pressed orsubjected to the application of an external pressure prior to and/orduring sintering. In some embodiments, metal halide particles aresintered under a pressure ranging from about 1 kpsi to about 200 kpsi.In some embodiments, the external pressure is applied uniaxially. Insome embodiments, the pressure is applied isostatically. In someembodiments, metal halide particles are sintered for a time periodranging from about 0.5 to 10 hours. In some embodiments, metal halideparticles are sintered for a time period ranging from about 1 hour toabout 6 hours. Additionally, in some embodiments, metal halide particlesare sintered under vacuum conditions or in an inert, dry atmosphere toprevent water absorption by hygroscopic metal halides.

In some embodiments, a method of producing a polycrystallinescintillator comprises providing a mixture comprising particles of afirst semiconductor having a first bandgap and particles of a secondsemiconductor having a second bandgap and sintering the mixture toprovide a polycrystalline scintillator material comprising a radiationabsorption region and spatially discrete radiative exciton recombinationregions. In some embodiments, the first bandgap is larger than thesecond bandgap.

In some embodiments, the radiation absorption region is formed from thefirst semiconductor particles and the spatially discrete radiativeexciton recombination regions are formed by the second semiconductorparticles. Semiconductor particles suitable for use in methods offoaming a polycrystalline scintillator can comprise any semiconductordescribed herein. Moreover, a mixture comprising particles of a firstsemiconductor and a second semiconductor can be sintered according tothe principles set forth hereinabove for sintering a mixture of metalhalide particles.

III. Crystalline Particles

In another aspect, crystalline particles or grains are described herein.In some embodiments, a crystalline particle or grain comprises aradiation absorption region comprising at least one metal halide and aspatially discrete radiative exciton recombination region. In someembodiments, the spatially discrete radiative exciton recombinationregion comprises a metal halide comprising one or more scintillationactivators. In some embodiments, the metal halide radiation absorptionregion of a crystalline particle described herein has less scintillationactivator than the spatially discrete radiative exciton recombinationregion. In some embodiments, the metal halide radiation absorptionregion of a crystalline particle described herein is free orsubstantially free of scintillation activator.

In other embodiments, a crystalline particle described herein comprisesat least one radiation absorption region and at least one spatiallydiscrete radiative exciton recombination region, the particle having asize ranging from about 20 nm to about 100 μm. In some embodiments, thecrystalline particle has a size ranging from about 50 nm to about 100 μmor from about 100 nm to about 100 μm. In some embodiments, thecrystalline particle has a size ranging from about 200 nm to about 50μm.

In some embodiments, the spatially discrete radiative excitonrecombination region of a crystalline particle described herein isdisposed between the radiation absorption region and an exterior surfaceof the crystalline particle. In some embodiments, for example, thespatially discrete radiative exciton recombination region is located atthe periphery of the crystalline particle surrounding a core comprisingthe radiation absorption region. In some embodiments, a crystallineparticle comprises a core radiation absorption region and a spatiallydiscrete shell radiative exciton recombination region.

FIG. 4 illustrates a cross-sectional view of a crystalline particleaccording to one embodiment described herein. As illustrated in FIG. 4,the crystalline particle (400) comprises a radiation absorption core(401) and a spatially discrete radiative exciton recombination shell(402) at least partially surrounding the core (401). In someembodiments, the spatially discrete radiative exciton recombinationshell (402) completely or substantially completely surrounds the core(401). As described herein, excitons generated by the absorption ofradiation by the core (401) are transferred to the spatially discreteshell (402) for radiative recombination and the release of photons.

In some embodiments wherein the spatially discrete radiative excitonrecombination region is disposed between the radiation absorption regionand an exterior surface of the crystalline particle, an excitonconfinement region or layer can be provided adjacent to the spatiallydiscrete radiative exciton recombination region. In some embodiments, anexciton confinement layer can preclude or inhibit excitons transferredto a spatially discrete radiative exciton recombination region fromundergoing non-radiative recombination at particle surface traps and/orsurface defects. Moreover, in some embodiments, an exciton confinementregion adjacent to a spatially discrete radiative exciton recombinationregion of a crystalline particle can protect the recombination regionfrom damage during sintering of the crystalline particle as describedherein. In some embodiments, an exciton confinement region has a bandgaphigher than the bandgap of the material forming the spatially discreteradiative exciton recombination region. In some embodiments, an excitonconfinement region can comprise the same material as the core radiationabsorption region. In some embodiments, an exciton confinement region isa different material than the core radiation absorption region.

FIG. 5 illustrates a cross-sectional view of a crystalline particlecomprising an exciton confinement region adjacent to a spatiallydiscrete radiative exciton recombination region according to oneembodiment described herein. As illustrated in FIG. 5, the crystallineparticle (500) comprises a radiation absorption core (501) and aspatially discrete radiative exciton recombination shell (502) at leastpartially surrounding the core (501). In some embodiments, the spatiallydiscrete radiative exciton recombination shell (502) completely orsubstantially completely surrounds the core (501). As described herein,excitons generated by the absorption of radiation by the core (501) aretransferred to the spatially discrete shell (502) for radiativerecombination and the release of photons. An exciton confinement regionor layer (503) is disposed adjacent to and at least partially surroundsthe spatially discrete radiative exciton recombination shell (502). Insome embodiments, the exciton confinement region (503) completely orsubstantially completely surrounds the spatially discrete radiativeexciton recombination shell (502).

While the particles illustrated in FIGS. 4 and 5 are spherical,crystalline particles described herein can have any shape includingspherical, substantially spherical, non-spherical, elliptical orpolygonal.

In some embodiments, the radiation absorption core can comprise anymetal halide described herein free or substantially free ofscintillation activator. In some embodiments wherein the radiationabsorption core comprises an alkali halide described herein, the corehas a size less than about 40 nm. In some embodiments, an alkali halidecore has a size ranging from about 1 nm to about 40 nm or from about 5nm to about 30 nm. In some embodiments, an alkali halide core has a sizeranging from about 10 nm to about 20 nm.

In some embodiments wherein the core comprises an alkaline earth halide,the core has a size less than about 500 nm. In some embodiments, analkaline earth halide core has a size ranging from about 10 nm to about500 nm or from about 50 nm to about 200 nm. In some embodiments, analkaline earth halide core has a size ranging from about 250 nm to about750 nm. In some embodiments, an alkaline earth halide core has a sizeranging from about 10 nm to abut 100 nm or from about 20 nm to about 80nm.

In some embodiments, wherein the core comprises a transition metalhalide, the core has a size less than about 5 μm or less than about 1μm. In some embodiments, a transition metal halide core has a sizeranging from about 100 nm to about 5 μm or from about 200 nm to about 1μm. In some embodiments, a transition metal halide core has a sizeranging from about 250 nm to about 750 nm.

In some embodiments, the radiation absorption core can comprise anysemiconductor material described herein. In some embodiments wherein thecore comprises a semiconductor material, core has a size less than about100 μm. In some embodiments, a semiconductor core has a size rangingfrom about 20 nm to about 10 μm or from about 50 nm to about 1 μm. Insome embodiments, a semiconductor core has a size ranging from about 100nm to about 750 nm.

In some embodiments of a crystalline particle, the spatially discreteradiative exciton recombination shell can comprise any metal halidedescribed herein comprising one or more scintillation activators. Insome embodiments, the spatially discrete radiative exciton recombinationshell comprises an alkali halide having one or more scintillationactivators described herein. In some embodiments wherein the spatiallydiscrete radiative exciton recombination shell comprises an alkalihalide having scintillation activator, the shell has a thickness up toabout 5 nm. In some embodiments, an alkali halide shell has a thicknessranging from about 1 nm to about 5 nm or from about 2 nm to about 4 nm.

In some embodiments, the spatially discrete radiative excitonrecombination shell comprises any alkaline earth halide described hereinhaving one or more scintillation activators. In some embodiments whereinthe spatially discrete radiative exciton recombination shell comprisesan alkaline earth halide having scintillation activator, the shell has athickness up to about 10 nm. In some embodiments, an alkaline earthhalide shell has a thickness ranging from about 1 nm to about 10 nm orfrom about 3 nm to about 7 nm.

In some embodiments, the spatially discrete radiative excitonrecombination shell comprises any transition metal halide describedherein having one or more scintillation activators. In some embodimentswherein the spatially discrete radiative exciton recombination shellcomprises a transition metal halide having scintillation activator, theshell has a thickness up to about 100 nm. In some embodiments, atransition metal halide shell has a thickness ranging from about 1 nm toabout 100 nm or from about 5 nm to about 75 nm. In some embodiments, atransition metal halide shell has a thickness ranging from about 10 nmto about 50 nm.

In some embodiments, the spatially discrete radiative excitonrecombination shell comprises a semiconductor material described hereinhaving a bandgap less than the bandgap of the core semiconductormaterial. In some embodiments wherein the shell comprises asemiconductor material, the shell has a thickness up to about 1 μm. Insome embodiments, a semiconductor shell has a thickness ranging fromabout 5 nm to about 1 μm or from about 10 nm to about 500 nm.

A crystalline particle having a spatially discrete radiative excitonrecombination region located at the periphery of the crystallineparticle surrounding a radiation absorption core region can be producedaccording to several methods. In some embodiments, a metal halideparticle can be doped at the periphery of the particle with one or morescintillation activators to provide the spatially discrete radiativeexciton recombination shell region and an undoped radiation absorptioncore region. In one embodiment, for example, a SrI₂ particle can bedoped at the periphery with Eu²⁺ activator to provide the spatiallydiscrete radiative exciton recombination shell and an undoped SrI₂radiation absorption core. In such embodiments, the crystalline particlecan demonstrate a gradient of scintillation activator wherein the amountof scintillation activator increases with increasing distance from theparticle center or core.

In some embodiments, a crystalline particle comprising a radiationabsorption core and a spatially discrete radiative exciton recombinationshell can be produced by providing host particles and diffusingscintillation activator into the host particles to a depth correspondingto the desired thickness of the spatially discrete radiative excitonrecombination shell. In one embodiment, for example, particles of SrI₂are provided and placed in an oven or furnace at elevated temperature. Avapor comprising scintillation activator, such as Eu²⁺, can be flowedover the SrI₂ particles at a temperature and time period sufficient todiffuse the scintillation activator into the SrI₂ particles to thedesired depth, thereby establishing a radiation absorption core and aspatially discrete radiative exciton recombination shell.

Alternatively, in some embodiments, a crystalline particle can beproduced by providing a metal halide particle free or substantially freeof scintillation activator and coating the metal halide particle with acomposition comprising scintillation activator. In such embodiments, thecoating can serve as the spatially discrete radiative excitonrecombination region and the metal halide particle can serve as theradiation absorption region. In some embodiments, for example, metalhalide host particles are provided and exposed to vapor comprisingprecursors of the metal halide host and one or more scintillationactivators to deposit a metal halide/scintillation activator coating onthe host particles. In some embodiments, such depositions can beadministered in chemical vapor deposition (CVD) apparatus or carried outin solution phase in liquid phase epitaxy apparatus.

In some embodiments wherein the radiation absorption region comprises afirst semiconductor, a spatially discrete radiative excitonrecombination region comprising a second semiconductor can be depositedon the first semiconductor. In some embodiments, the secondsemiconductor is grown on the first semiconductor by one or moreepitaxial methods such as chemical vapor deposition (CVD), atomic layerepitaxy (ALE), solution atomic layer epitaxy (SALE) or molecular beamepitaxy (MBE).

In some embodiments, the foregoing construction of a crystallineparticle can be reversed wherein the spatially discrete radiativeexciton recombination region is provided as the particle core, and theradiation absorption region is disposed at the periphery of the particleat least partially surrounding the core. In some embodiments, theradiation absorption region is provided as a shell around a spatiallydiscrete radiative exciton recombination core.

In some embodiments, crystalline particles described in this section(section III) of the application can be sintered to provide apolycrystalline scintillator material having at least one radiationabsorption region and at least one spatially discrete radiative excitonrecombination region. In some embodiments, the construction of thecrystalline particles provides the polycrystalline scintillator aplurality of radiation absorption regions and a plurality of spatiallydiscrete radiative exciton recombination regions.

In some embodiments, a method of producing a scintillator comprisesproviding crystalline particles comprising a radiation absorption regionand a spatially discrete radiative exciton recombination region andsintering the crystalline particles to provide a polycrystallinescintillator material. The crystalline particles sintered to provide thepolycrystalline scintillator material can have any constructiondescribed in this section (section III) of the application.

The crystalline particles can be sintered under any conditions oftemperature, pressure and time effective to provide a sinteredpolycrystalline scintillator having a construction described herein.Sintering conditions can be determined according to several factorsincluding specific identity of the metal halide or semiconductormaterial, particle size and particle shape. Moreover, sintering shouldbe administered at temperature that does not induce substantialmigration or diffusion of scintillation activator out of a spatiallydiscrete radiative exciton recombination region and into the radiationabsorption region.

In some embodiments, for example, crystalline particles comprising aradiation absorption region and a spatially discrete radiative excitonrecombination region are sintered at a temperature below the meltingpoint of the particles. In some embodiments, metal halide crystallineparticles described herein are sintered at a temperature ranging fromabout 30° C. to about 650° C. In some embodiments, sintering temperaturecan be ramped at any desired rate. In some embodiments, the temperatureis ramped at a rate ranging from about 1° C./min to 10° C./min.

Moreover, in some embodiments, crystalline particles are pressed orsubjected to the application of an external pressure during sintering.In some embodiments, crystalline particles are sintered under a pressureranging from about 1 kpsi to about 200 kpsi. In some embodiments, theexternal pressure is applied uniaxially. In some embodiments, thepressure is applied isostatically. In some embodiments, crystallineparticles are sintered for a time period ranging from about 0.5 to 10hours. In some embodiments, crystalline particles are sintered for atime period ranging from about 1 hour to about 6 hours. Additionally, insome embodiments, crystalline particles are sintered under vacuumconditions or in an inert, dry atmosphere to prevent water absorption byhygroscopic metal halides.

In some embodiments, the resulting polycrystalline scintillator materialhas a density of at least about 97% or at least about 99%.

IV. Scintillation Detector

In another embodiment, the present invention provides a scintillationdetector or counter comprising and an electromagnetic radiation sensor,wherein the scintillator comprises at least one radiation absorptionregion and at least one spatially discrete radiative excitonrecombination region for receiving excitons from the at least oneradiation absorption region. A scintillator of any constructiondescribed herein can be used in a scintillator counter. In someembodiments, an electromagnetic radiation sensor comprises aphotomultiplier tube (PMT) or a photodiode. An electromagnetic radiationsensor, in some embodiments, is operable to detect visible radiation,infrared radiation, ultraviolet radiation or combinations thereof.

V. Methods of Producing Scintillators

In another aspect, methods of producing scintillators are describedherein. In some embodiments, a method of producing a scintillatorcomprises providing a radiation absorption region comprising a firstmaterial having a first bandgap and locally modulating the first bandgapto trap excitons in a spatially discrete radiative exciton combinationregion, wherein locally modulating the first bandgap comprises providingthe radiative exciton recombination region in electrical communicationwith the radiation absorption region, the radiative excitonrecombination region comprising a second material having a secondbandgap different from the first bandgap.

In some embodiments, the second bandgap is smaller or of lower energythan the first bandgap. In some embodiments, the first materialcomprises a metal halide free or substantially free of a scintillationactivator and the second material comprises a metal halide havingincorporated therein one or more scintillation activators as describedherein. FIG. 6 illustrates the electronic structure of a scintillatorcomprising a metal halide radiation absorption region and a spatiallydiscrete metal halide radiative exciton recombination region comprisingscintillation activator according to one embodiment described herein. Asillustrated in FIG. 6, the scintillation activator localized to theradiative exciton recombination region provides energy or dopant levelsfacilitating the acceptance of electron and hole carriers from the metalhalide radiation absorption region for radiative recombination.

Additionally, in some embodiments, a method of producing a scintillatorcomprises providing a radiation absorption region comprising a metalhalide free or substantially free of a scintillation activator andproviding a spatially discrete radiative exciton recombination region inelectrical communication with the radiation absorption region, theradiative exciton recombination region comprising a metal halidecomprising one or more scintillation activators. In some embodiments,the metal halide radiation absorption region is single crystalline, andthe spatially discrete radiative exciton combination region comprises aphase of metal halide comprising scintillation activator within thesingle crystal. In some embodiments, for example, phases of metal halidecomprising activator are precipitated from the single crystalline phasewhile cooling the metal halide crystal from melt.

Moreover, in some embodiments, polycrystalline scintillators can beproduced according to the methods disclosed in sections II and IIIhereinabove.

In another aspect, the present invention provides methods of convertingradiation of a first energy into radiation of a second energy. In oneembodiment, a method of converting radiation of a first energy intoradiation of a second energy comprises providing a scintillatorcomprising at least one radiation absorption region and at least onespatially discrete radiative exciton recombination region, absorbing theradiation of the first energy in the radiation absorption region togenerate excitons and recombining at least some of the excitons in thespatially discrete radiative exciton recombination region to emitradiation of a second energy. In some embodiments, the radiation of thefirst energy has a wavelength less than the wavelength of the radiationof the second energy. As described herein, in some embodiments, theradiation absorption region of the scintillator comprises a metal halidefree or substantially free of a scintillation activator, and thespatially discrete radiative exciton recombination region comprises ametal halide comprising one or more scintillation activators.

In a further aspect, the present invention provides a method of reducingnon-proportional response in a scintillator. In one embodiment, a methodof reducing non-proportional response comprises providing a scintillatorcomprising at least one radiation absorption region and at least onespatially discrete radiative exciton recombination region, absorbingradiation of a first energy in the radiation absorption region togenerate excitons, transferring at least some of the excitons out of theradiation absorption region and into the spatially discrete radiativeexciton recombination region and recombining the excitons to emitradiation of a second energy from the radiative exciton recombinationregion. In some embodiments, the radiation absorption region of thescintillator comprises a metal halide free or substantially free of ascintillation activator, and the spatially discrete radiative excitonrecombination region comprises a metal halide comprising one or morescintillation activators.

Various embodiments of the invention have been described in fulfillmentof the various objectives of the invention. It should be recognized thatthese embodiments are merely illustrative of the principles of thepresent invention. Numerous modifications and adaptations thereof willbe readily apparent to those skilled in the art without departing fromthe spirit and scope of the invention.

That which is claimed is:
 1. A crystalline particle comprising: aradiation absorption region comprising at least one metal halide; and aspatially discrete radiative exciton recombination region operable toreceive excitons produced in the radiation absorption region, thediscrete radiative exciton recombination region having a size of 1 nm to10 nm and the radiation absorption region having a size of 10 nm to 500nm, wherein the spatially discrete radiative recombination region isdisposed between the radiation absorption region and an exterior surfaceof the crystalline particle.
 2. The crystalline particle of claim 1,wherein the spatially discrete radiative exciton recombination regioncomprises a metal halide comprising one or more scintillationactivators.
 3. The crystalline particle of claim 1, wherein thespatially discrete radiative exciton recombination region is a shell atleast partially surrounding the radiation absorption region.
 4. Thecrystalline particle of claim 1, wherein the metal halide comprises analkali halide, an alkaline earth halide or a transition metal halide. 5.The crystalline particle of claim 4, wherein the alkali halide comprisescesium iodide, sodium iodide or potassium iodide.
 6. The crystallineparticle of claim 5, wherein the spatially discrete radiative excitonrecombination region comprises an alkali halide comprising a thalliumscintillation activator.
 7. The crystalline particle of claim 4, whereinthe alkaline earth halide comprises strontium iodide, barium iodide orbarium bromide iodide.
 8. The crystalline particle of claim 7, whereinthe spatially discrete radiative exciton recombination region comprisesan alkaline earth halide comprising a europium scintillation activator.9. The crystalline particle of claim 4, wherein the metal of thetransition metal halide is selected from the group consisting ofmetallic elements of Groups IB, IIB, IIIB, IIIA, IVA and VA of thePeriodic Table.
 10. The crystalline particle of claim 1, wherein theradiation absorption region comprises strontium iodide and the spatiallydiscrete radiative exciton recombination region comprises strontiumiodide comprising a europium scintillation activator.
 11. Thecrystalline particle of claim 1 further comprising an excitonconfinement region adjacent to the spatially discrete radiative excitonrecombination region.
 12. A crystalline particle comprising: radiationabsorption region comprising strontium iodide; and a spatially discreteradiative exciton recombination region operable to receive excitonsproduced in the radiation absorption region, the discrete radiativeexciton recombination region comprising strontium iodide having aeuropium scintillation activator, wherein the spatially discreteradiative recombination region is disposed between the radiationabsorption region and an exterior surface of the crystalline particle.13. The crystalline particle of claim 12, wherein the discrete radiativeexciton recombination region has a size of 1 nm to 10 nm and theradiation absorption region has a size of 10 nm to 500 nm.
 14. Thecrystalline particle of claim 12 further comprising an excitonconfinement region adjacent to the spatially discrete radiative excitonrecombination region.
 15. The crystalline particle of claim 12, whereinthe spatially discrete radiative exciton recombination region is a shellat least partially surrounding the radiation absorption region.
 16. Thecrystalline particle of claim 12, wherein the radiation absorptionregion has a carrier mobility of 1×10⁴ cm²/V·s to 1000 cm²/V·s.
 17. Thecrystalline particle of claim 12, wherein the europium scintillationactivator is present in the discrete radiative recombination region inan amount of 0.1 mol % to 10 mol %.
 18. The crystalline particle ofclaim 12 comprising a plurality of the spatially discrete radiativeexciton recombination regions.
 19. The crystalline particle of claim 12,wherein the radiation absorption region is single crystalline.